Carbohydrate solutions



Patented May 22,- 1945 NlTED s'm'r zs 2,376,743 CARBOHYDRATE SOLUTIONS Bruno Wendt, Dessau, Germany; vested in the Alien Property Custodian No Drawing. Application January 4, 19451, Serial No. 373,185. In Germany December 19, 1939 6 @laims. (Cl. 106-162) My present invention relates to carbohydrate solutions and more particularly to the change in viscosity of such solutions.

It is an object of my invention to provide a process for increasing the viscosity of aqueous carbohydrate solutions.

Another object is the provision of a process for increasing the viscosity of organic carbohydrate solutions containing water.

Further objects of my inventionwill become apparent from the following description.

I have found that the viscosity of solutions containing carbohydrates or derivatives thereof such as glucose, dextrine, starch (arrow root), or derivatives of cellulose can be increased by adding compounds having a substantive character. It is noted that solutions containing only these compounds in amounts as used according to the invention do not possess a perceptible vis-,

cosity compared with the increase of viscosity which they effect.

The change in viscosity does not depend only phenyleneoxide hydroxycarboxylic acids, diphenon the nature of the added substance but on that of the substratum. It has been found that the viscosity of substances which are very viscous is effected more appreciably than the viscosity of compounds which yield weakly viscous solutions as, for instance, sugar and dextrine. If, however, concentrated solutions of the latter compounds are used the reached increase of viscosity can already be distinguished with the. naked eye. Solutions of high-Viscous derivatives of cellulose such as methylcellulose or hydroxyalkylcellulose can even be converted into solid jellies by adding substantive substances.

Attempts have shown that the eiiiciency of the added substances is decreased if electrolytes are present. It is therefore advantageous to use solutions containing at most a small'amount of electrolytes.

All known substantive compounds can be used bis- (2,3-hydroxynaphthoyl) -diaminostilbene, bis- (1,2-hydroxynaphthoyl)-benzidine, arylides of '7- hydroxynaphthalene-l-carboxylic acid, furtherylenesulfide hydroxycarboxylic acids, 3-hydroxy diphenyl-aminocarboxylic acid, hydroxychrysene carboxylic acid, hydroxyfluorene carboxylic acid,

hydroxyphenanthrene carboxylic acid and hydroxynaphthazone, hydroxytriazoles and similar heterocyclic compounds.

Moreover, colorless compounds are valuable which contain special groups capable of rendering the compound substantive. Such groups are often described as constituents of azo dyestufis (confer, for instance, Kolloidchemische Beihefte, vol. 34, p 218; 1931). Compounds containing such groups are also employed as diazoor coupling components for forming dyestuff with the fiber as described in many patent specifications. Groups adapted to render substances substantive are, for instance, derived from the following compounds:

Benzidine and derivatives thereof, diaminofluorene, diamino-diphenyleneoxidc, diamino-diphenylenesulfide, diamino-carbazole, 1,4- and 1,5- naphthylenediamines, diaminodiphenylamine, diaminostilbene, diaminodiphenylurea, diaminodiphenylthiourea, compounds which contain several groups of aminobenzoyl or several similar groups. Furthermore, substances are suitable which contain the group of aminonaphthol or derivatives thereof as, for instance, 2-amino-5-naphthol-7- sulfo acid, 1-amino-5-naphthol-7-sulfo acid and derivatives thereof, for instance a1ky1-, phenyl-, benzoyl-, aminobenzoyl-, aminobenzoyl-aminobenzoyl-compounds and ureas thereof. Moreover, the arylides of acetoacetic acid, cyanacetic acid, oxalacetic acid, acetonedicarboxylic acid, benzoylacetic acid, terephthalacetic acid, naphthoylacetic acid, hydroxynaphthoylacetic acid and similar compounds are substantive. Of the heterocyclic rings which render compounds substantive the following rings are for instance suitable: thiazole, triazole and imidazole rings. Compounds with such rings are, for instance, dehydrothiotoluidine, the sulfo acid thereof and similar compounds, triazoles and imidazoles of aminonaphtholsulfo acids and 1,3,5-triazine compounds. These classes of compounds, for instance, include products obtained by reacting 1 mol of benzidine-disulfo acid, diaminostilbenedisulfo acid or diaminodiphenylureadisulfo acid with two mols of cyanurchloride and subsequently saponifying the chlorine atoms. Instead of the saponification a reaction with aniline or other aliphatic, aromatic hydroaromatic or heterocyclic amines or hydroxy compounds may also be carried out, whereupon, if desired, the chlorine not 'The substantive compounds may, moreover, be and hydroxy1 so that the costs of preparation are lower than (b) reacted is saponifled. The following compounds The more detailed practice of the invention are especially suitable: is illustrated by the following example. There soiNs (1) BOINB CH3 7 /CH| g |\NO O-NHOCH=CH NH-C -C N\ C: 7 CH:

so-N SONS HO-Csfla /C:HOH N-O-c 0-NH NH-C 0 'N\ H0'c3Ht oimoa BOINB (3) OlNE N\ I no-c \GNHOCONH NH-COO'NHKIE/ Ell-OH 1% 1 N N on v ()H (4) are of course many forms of the invention'other N SOlNB SOtNB N than this specific embodiment.

a-o \O-NHOCHAJH NH-(IJ/ -a" Example 1% 1 1 N N 7.5 grams of medium-viscous Tylose a prof prietary methyl cellulose are dissolved in 900 co. m of water. To this mixture a solution is added R which consists of 100 cc. of water and 1.5 grams wherein It, R, R" and R' represent hydroxyl of a compound corresponding to the following or a monovalent organic radical, for instance, of formula: isoamylamine, di-oxethylamine, dodecylamine, cyclohexylamine, aniline, chloroaniline, anisidine, N p-cyclohexylaniline, phenol, thiophenol, amino- R-C C-NH om n benzthiazole or aminobenzimidazole. Q, 1 1

The substantive compound may be mixed with the water before or after the addition to the water of the carbohydrate. In the former in- R.

stance a very high speed of solution is attained. wherein R and are the radical of aniline and A sizing product is thus added in the production of the colloid, for mobtained which is of, a property similar to that stance, during its precipitation or desiccation. of a mduct madei usual In Her 23 Thus products are obtained which from the outof T5056 and 1000 2 i from grams set contain substances capable of increasing the I claim: zfig s 1 :gfgi tgz z z gggg ggig g 1. A process for increasing the viscosity of a r main th m t eth in dr c6 diti n The solution of the member of the group consisting g gg fg to d d nd of water-soluble carbohydrates and cellulose de- 31 1? on nature and that of the colloid ag well r1Vim-ves soluble m solvents containing as on the viscosity desired Favorable effects are stantlal amount of water said solution contain reached when the quantity of the substantive mg a substantial amount of water and at most a small amount of electrolytes, which comprises compound amounts to 225% of the quantity of the colloid. Besides the carbohydrates above ad to Sam solution tmzme denvatwe mentioned other carbohydrates may also be used, g at g ggg g cglored one of the groups for instance fructose or cane sugar. 0 co poun 00 g o Theproducts prepared by using derivatives of N cellulose are especially valuable. Useful deriva- O tives of cellulose are, for instance, m'ethylcelluii loses, hydroxyalkylcelluloses, and acetylcelluloses N extensively hydrolyzed such as acetyl-celluloses c soluble in aqueous acetone of 40% strength. of 0 A the colorless or slightly colored substances serv- (a)- ing to increase the viscosity those compounds are important which are neither diazotizable nor capable of coupling. The mixtures or solution 110-? O of the colloids and added substances may be used, N N

for instance, for the preparation of finishing and sizing products. In this case a considerable peri centage of derivative of cellulose is saved 0 SOlNa SOsNa SOiNa those of the products hitherto employed and hav- 70.

N ing the same viscosity. The substantive com- R-C/ \G-NH cn=cn Nil-0 \C-R" pounds may also serve to regulate the viscosity l of spinning solutions. Instead of acetone other solvents for derivativw of cellulose may be used, 0 for instance dioxane. 76 {1' R"! wherein R, R, ,R'Qand R'" represent hydroxyl or a monovalent organic radical.

2. A solution of a member of the group consisting of water-soluble carbohydrates and cellulose derivatives solulile in solvents containing a substantial amount of water, said solution containing a substantial amount of water, at most a small amount of electrolytes and a 1,3,5-triazine which is at most slightly colored one of the group wherein R, R, R" and R' representhydroxyl or a monovalent organic radical.

3. The process as defined in claim lin which said 1,3,5-trlazlne derivative is a compound having the following formula:

SOaNfl I on ' SOsNfl 4. A process as defined in claim 1 in which said 1,3,5-triazine derivative is a compound having the following formula: I

I SOiNB S0;Na

wherein R, R, R" and R' represent hydroxyl or a monovalent organic radical.

5. A solution as defined in claim 2 in which said 1,3,5-triazine derivative is a compound having the following formula:

5 e. A solution as defined in claim 2 in which said 1,3,5-trlazine derivative is a compound having the following formula:

some SOzNB N a- (ii-NH CH=CH NH-(IJ/ r l-n" wherein R, R, R" and R'" represent hydroxy or a monovalent organic radical.

BRUNO WENDT. 

